Copolymers of nu-(acylamidomethyl)-acrylamides



United States Patent C COPOLYMERS F N-(ACYLAMIDOMETHYL)- ACRYLAMIDESNeal 0. Brace, Woodstown, NJ assignor to E. I. du Pont de Nemours andCompany, Wilmington, Dei., a corporation of Delaware N0 Drawing. FiledApr. 28, 1955, Ser. No. 504,678

6 Claims. (Cl. 260--86.1)

use as water repellents for a wide variety of textile fabrics includingcotton, wool and the new hydrophobic fibers. However, none of them hasbeen found to be entirely satisfactory since they have been found to beeither too expensive or else they exhibit poor durability and are notsufficiently hydrophobic.

It is an object of this invention to provide new derivatives ofacrylamides and polymers thereof which are capable of imparting adurable, water-repellent finish to textile fabrics. A further object isto provide a process for the preparation of these new acrylamides andpolymers thereof. Other objects will appear hereinafter.

These and other objects are accomplished by the new acrylamides havingthe formula:

wherein R is a saturated, aliphatic, hydrocarbon radical of from 10 tocarbon atoms and R is a radical selected from the group consisting ofhydrogen and methyl radicals. The homopolymers and copolymers of theabove recited acrylamides are easily prepared by the use of a freeradical initiator.

The N(acylamidomethyl)acrylamides of the present invention are preparedby allowing an N-methylol acrylamide to react with an acrylamide in thepresence of a strong acid catalyst and usually in an organic solvent.After the acid is neutralized, the product is isolated and is preferablywashed with water to remove the salt and unreacted acrylamide orN,N'-methy1enebisacrylamide. The acrylamides arehigh-melting,crystalline, white solids which are soluble in a variety of commonorganic solvents. They are sufficiently stable to be recrystallized, anddo not decompose readily to give formaldehyde, nor are they readilyhydrolyzed. The vinyl groups of the acrylamides are highly'activated andpolymerization is effected quite readily by contact with a free radicalinitiator such as a,a'-azobisisobutyronitrile.

After polymerization, the polymers are obtained from solution asnon-crystalline solids, higher melting than the mononiers. They do notpossess sharp melting points, but soften gradually over the range ofabout 190 to 250 C. They may be redissolved and precipitated in order toremove any impurities such as initiator fragments. Filmscan be cast fromtheir solutions. 7

The following examples will better illustrate the nature of the presentinvention; however, the invention is not intended to be limited to theseexamples. Parts are by Weight unless otherwise indicated.

Example 1.N(stearamid0methyl) methacrylamide In a 500 cc. flask wasplaced 12.75 g. (0.15 m.) methacrylamide, 10.0 g. water 15.0 g. (0.05m.) purified N-methylolstearamide (M.P. 112 C., from technical lyst andstirring continued for 2 hours.

grade stearamide) and cc. methylethyl ketone, Technical grade stearamidecontains approximately equal amounts of palmitamide and stearamide. Thereaction mixture was stirred and heated to 60 C. and acidified with 24%isopropyl alcoholic hydrochloric acid solution to a pH of about 1-2 overa period of 6 hours. The mixture became an almost clear solution. It wasdiluted with 100 cc. acetone and filtered hot.

tone and air dried. It weighed 11.0 g. (58% of theory) and had M.P. (S-)108-110 C. When recrystallized from a mixture of acetone and methylethylketone, it had M.P. (S-105) 111-113 C. It depressed the M.P.

of methylolstearamide to give M.P. (S-105) 108-109 C.,

and had a distinctive LR. spectrum. An ethyl alcohol solutiondecolorized permanganate solution.

Analysis.Calcd. for C H N O C, 72.10; H, 11.55; V

N, 7.64%. Found: C, 71.0; H, 11.5; N, 7.3%.

Example 2.-N(stearamid0methyl)acrylamide In a 2-liter flask was placed71.0 g. acrylamide (1.0 m.), 1,000 cc. methylethyl ketone, g. (0.5 m.)technical N-methylolstearamide and the mixture heated to 60 C. withstirring in a constant temperature bath.

Technical N-methylolstearamide is prepared from technical gradestearamide which contains approximately equal amounts of palmitamide andstearamide. The mixture was made acid to Clayton Yellow paper (pH 1-2)by the addition of 4 cc. of concentrated hydrochloric acid. The mixturegrew thick over a 5-hour reaction period.- The acid was neutralized bysodium carbonate solution and the solid filtered at 40 C. on a Buchnerfunnel. The product when dry weighed 142.8 g. and had M.P. 150- 151 C.This is a 77% yield.

Analysis.Calcd. for C H N O C, 71.58; H, 11.44; N, 7.95%. Found: C,71.7; H, 11.59; N, 7.5%.

Example 3.N( lauramidomethyl) acrylamide cc. methylethyl ketone, andthen 300 cc. water. The airdried solid weighed 28.9 g. (86% of theory)and had M.P. (S450) 153-154" C. On recrystallization from hot benzene,it melted at 157157.5 C. A mixed M.P.

Analysis.Calcd. for CwHgoNzOzi C, H,

N, 9.96%. Found: (3.68.4; H, 10.5; N, 9.4%. g

Example 4.-P0lymer 0f N(stearamid0methyl)acrylamide Five grams of thecompound of Example 2 in 100 cc. dry benzene was heated to 78 C. to givea solution. oz,oc'-AZOblSlSOlJLllYrOIlltl'ilfi (0.25 g.) was added as acata- Some polymer had formed. Another 0.25 g. catalyst was added andheating and stirring continued for a total of 22 hours. The product wasa soft gel in benzene. It was soluble in hot chloroform, insoluble inboiling acetone. The dried polymer weighed 5.0 g. and had a M.P. (S183)03-218 C. The chloroform solution was viscous when cool and gave abrittle film when evaporated. The polymer was analyzed.

Found: C, 72.4; H, 11.8; N, 7.1%.

Cotton poplin fabric impregnated with a solution of 1.0 g. of thepolymer in 50 cc. chloroform had an in- Patented Dec. 21, 1960 Thefiltrate deposited solid which was collected, washed with coldacecreasein dry weight of 1.2%. Water repellence was determined by sprayratings in the standard AATCC test. Before curing the fabric had an 80spray rating, and curing at 180 C. gave a 100 rating.

Example 5.-Coplymer of N (stearamidomethyl)acrylamide andN(lauramidomethyl)acrylamide Ten grams of N(stearamidomethyl)acrylamideof Example 2 (not washed with water and probably containing a littleN,N'-methylenebisacrylamide), g. N(lauramidomethyl)acrylamide of Example3, 100 cc. dry benzene and 0.50 g. a,a'-azobisisobutyronitrile wereplaced in a fiask under nitrogen. The mixture was heated to reflux.Polymerization was rapid, giving a viscous gel in a few minutes. Morebenzene was added, but the polymer was too viscous to dissolve. TheIIllX- ture was cooled and the gel scraped out of the flask. The polymerwas precipitated by the addition of 300 cc. methanol. The polymerweighed 18.5 g. and melted at 202-210 (clear) to 220 C. where it beganto flow.

Example 6.C0p0lymers of N (stearamidomethyDacrylamide with textile resinmonomers A slurry of the compound of Example 2 and another comonomer in250 cc. benzene under nitrogen atmosphere was heated to 80 C. whilestirring until a clear solution was formed. A solution of a,a'-aZOblSiSObutyronitrile in benzene was added and stirring continued for 4 hours.Benzene was removed by vacuum distillation during the last 2 hours.

The following table indicates the comonomers and proportions used andthe properties of the copolymers obtained. When the resulting polymerswere tested according to the procedure of Example 4, they all showed aspray rating after curing of 100.

TABLE I Copolymers of n(stearamidomethyl)acrylamide with other monomersThe acrylamides of the present invention are primarily useful asintermediates for the preparation of polymers. These polymers exhibit anexcellent, durable water-repellent effect on nylon. The polymers arealso useful as water-repellents for cotton and other cellulosictextiles. Their effect on cotton and other cellulosic textiles can bemade durable by the formation of copolymers with other textileresin-forming monomers. These textile resin-forming monomers areexemplified by glycidyl methacrylate and rnethylol acrylamide, both ofwhich contain functional groups which can react with the hydroxyl groupsof cellulose or can cross-link adjacent polymer molecules on the fabricsurface. Copolymers of 5, 10 or 20 moles ofN(stearamidomethyl)acrylamide with 1 mole of either of these monomers,give initial spray ratings of 100 after curing, and 70-90 even '4 after3 aqueous soap washes. Copolymers of fi-dimethylaminoethyl methacrylatequaternized with methyl iodide are also operable.

The polymers can also be coapplied from the same or a separate bath withother resin-forming monomers such as a melamine-formaldehyde resin. Theacrylamide polymer is water-insoluble, and so is generally applied froman organic solvent bath. Thus, in the twobath system, it is possible toapply the melamine-formaldehyde from an aqueous bath.

By the coapplication of a conventional melamineformaldehyde resin, it ispossible to maintain a spray rating even after 3 aqueous soap washes.

The water repellent efiect of these polymers can also be improved by theanchor coat method. It has been found that whenpoly-fl-methacrylyloxyethyldiethylmethyl ammonium stearate (as moreparticularly disclosed in US. Patent No. 2,741,568) is applied followedby poly-N(stearamidomethyl)acrylamide, the durability to washing isimproved greatly.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

What is claimed is:

1. A copolymer derived by polymerizing from 5 to 20 molecular parts of acompound having the general formula:

wherein R is a saturated aliphatic hydrocarbon radical of from 10 to 20carbon atoms and R is a radical selected from the group consisting ofhydrogen and methyl radicals, with 1 molecular part of a monomerselected from the group consisting of glycidyl methacrylate andN-hydroxymethylacrylamide.

2. A copolymer derived by polymerizing from 5 to 20 molecular parts ofN-(lauramidomethyl)acrylamide with 1 molecular part of glycidylmethacrylate.

3. A copolymer derived by polymerizing from 5 to 20 molecular parts ofN-(lauramidomethyl)acrylamide with 1 molecular part ofN-hydroxymethylacrylamide.

4. A copolymer derived by polymerizing from 5 to 20 molecular parts ofN-(stearamidornethyl)acrylamide with 1 molecular part of glycidylmethacrylate.

5. A copolymer derived by polymerizing from 5 to 20 molecular parts ofN-(stearamidomethyl)acrylamide with 1 molecular part ofN-hydroxymethylacrylamide.

6. A copolymer derived by polymerizing from 5 to 20 molecular parts ofN-(stearamidomethyl)methacrylamide with 1 molecular part ofN-hydroxymethylacrylamide.

References Cited in the file of this patent UNITED STATES PATENTS2,259,650 Maxwell Oct. 21, 1941 2,279,497 Sallmann et al. Apr. 14, 19422,425,392 Robinson Aug. 12, 1947 2,478,378 Dickey Aug. 9, 1949 2,606,810Erickson et al. Aug. 12, 1952 2,680,110 Loughran et al. June 1, 19542,827,397 Afileck Mar. 18, 1958 2,885,438 Parret et al. May 5, 1959OTHER REFERENCES Magat et al.: 73 J.A.C.S. 1036 (March, 1951).

1. A COPOLYMER DERIVED BY POLYMERIZING FROM 5 TO 20 MOLECULAR PARTS OF ACOMPOUND HAVING THE GENERAL FORMULA: